Aziridinyl siloxanes



United States Patent 3,243,429 AZIRIDINYL SILOXANES George E. Ham, LakeJackson, Tex., assignor to The Dow Chemical Company, Midland, Mich., acorporation of Delaware No Drawing. Filed Nov. 13, 1963, Ser. No.323,240 5 Claims. (Cl. 260239) This invention relates to newcompositions of matter and to methods for the preparation of suchcompositions. More particularly, the present invention relates totrialkoxysilanes which contain both a carboxylic acid ester group and inaziridinyl group in the molecule, and to the preparation of suchcompounds.

Silicon compounds which contain an aziridinyl group directly bonded tothe silicon atom are known. Such compounds are disclosed, for example,by Heyna et al. in German Patent 834,990.

It has now been found that complex silicon compounds containing both acarboxylic acid ester group and an aziridinyl group in the molecule maybe prepared according to the following reaction wherein each R may bethe same or different and each represents an alkyl group of from 1 to '3carbon atoms, R and each R is a hydrogen atom or an alkyl group of from1 to 3 carbon atoms (i.e., the group {-C Hzk- H where k is an integer offrom 0 to 3) and each R is independently selected from the groupconsisting of the venience, the process is usually conducted atatmospheric pressure under reflux conditions, although sub-atmosphericand superatmospheric pressures may be employed if desired. It ispreferable to use an excess of aziridinyl compound so that the moleratio of aziridinyl compound to silicon compound is at least 1:1. dinylcompound to silicon compound of up to :1 may be used. As used herein,the term aziridinyl is meant to include both substituted andunsubstituted groups of the formula 0 wherein each R is selected fromthe group consisting of the hydrogen atom and a lower alkyl group offrom 1 to 4 carbon atoms. Examples of suitable solvents which may beused include the lower alkanols such as metha- Mole ratios of aziri-'I101, ethanol, n-plropanol, i-propanol, etc. or inert hydrocarbons suchas benzene, toluene, hexane, etc.

Examples of the reaction upon which the process of the invention isbased include the following:

The 3-(trialkoxysilyl)propyl esters of cap-unsaturated acids used asstarting materials in the process of the invention may be obtained bythe addition reaction of a trialkoxysilane and an allyl ester of ancap-unsaturated acid. For example, 3-(trimethoxysi1yl) propylmethacrylate may be prepared by reacting trimethoxysilane with allylmethacrylate in the presence of a silane addition catalyst.

The reaction may be represented by the following equation:

The compounds of the invention are useful for the formation of polymerswhich may be used to form laminates (metal, wood, plastic) and moldedarticles. In the presence of an acid, polymerizationmay be conducted,

through the aziridinyl group. In addition, the compounds (in eitherconcentrated formor in dilute solutions or dispersions) are useful asbactericides and have been found to inhibit or prevent the growth of E.coli.

The following examples are submitted for the purpose of illustrationonly and are not to be construed as limiting the scope of the inventionin any way.

Example I A mixture of 20.0 grams of the compound CH3 0 CH CHO-i-CHzCH2CH20i J( =CH1 [3-trimethoxysilyl)propyl methacrylate] and 200milliliters (about 170 grams) of ethylenimine was refluxed (temperatureabout 58 C.) for 18 hours. After this time, the excess ethylenimine wasremoved under vacuum, leaving 22.0 grams (a yield of 94 percent oftheory) of light yellow liquid aziridinyl compound. The product had aninfrared spectrum consistent with the following structure:

Distillation of the product resulted in considerable decomposition andpolymerization.

The purified product (2.3 grams collected prior to decomposition) hadthe following properties:

Boiling point 100-l0=2 C. at 0.06 mm. of Hg. Refractive index 1.4420 (20O, Na D line).

Density The infrared spectrum was identical to that for the crudeproduct.

Example 11 The following reaction mixture was heated at reflux for 1.5hours (-58 C.) and then allowed to stand at room temperature for about16 hours:

(a) 20.0 grams of [3- (trimethoxysilyl) propyl methacrylate] (b) 20.0milliliters of methanol, and

(c) 200.0 milliliters (about 170. grams) of ethylenimine.

The excess ethylenimine and methanol were removed under vacuum, leaving22.5 grams (a yield of 96 percent of theory) of the aziridinyl siloxaneproduct which of the same structure as the product of Example I(identified by infrared analysis).

Example 111 The product of Examples I and II were streaked onto petridishes containing nutrient agar which had been streaked with thebacteria E. coli. After incubation for 48 hours at room temperature, itwas noted that bacteria readily grew over the inoculated portions of thesurface of each plate in every place except where the test compounds hadbeen streaked.

1.062 at 20 C. i

4 I claim as my invention: 1. A compound of the formula wherein:

(a) each R group is an alkyl group of from 1 to 3 carbon atoms,

(b) R is the group (C H H where k is an integer of from 0 to 3, and

(c) each R is independently selected from the group consisting of thehydrogen atom and a lower alkyl group of from 1 to 4 carbon atoms.

3. A compound of the formula 0 R H no R0- ('1- 0 3 ft wherein each R isindependently selected from the group consisting of the hydrogen atomand a lower alkyl group of from 1 to 4 carbon atoms.

4. A compound of the formula wherein each R group is an alkyl group offrom 1 to 3 carbon atoms and m is an integer from 0 to 4.

5. The compound:

CH3O CH3. CH2 CH 0i- CHn -0-C( JOH2-N References Cited by the ExaminerHouben-Weyl: Methoden der Organischen Chemie, vol.

11/2 (Stuttgart, 1958), pages 242-244.

HENRY R. JILES, Primary Examiner.

A. D. ROLLINS, Assistant Examiner.

1. A COMPOUND OF THE FORMULA